1020071-98-0Relevant articles and documents
Modification of iron(II) tridentate bis(imino)pyridine complexes by a boryl group for the production of α-olefins at high temperature
Ionkin, Alex S.,Marshall, William J.,Adelman, Douglas J.,Fones, Barbara Bobik,Fish, Brian M.,Schiffhauer, Matthew F.
, p. 1902 - 1911 (2009/02/02)
A new series of boryl-substituted bis(imino)pyridine ligands [o-PinacolB-Ph-N=C(Me)-Py-C(Me)=N-Ph-o-BPinacol], Pinacol = (-O-(Me) 2C-C(Me)2-O-) (6), [2,4,6-tri-Me-Ph-N=C(Me)-Py-C(Me)=N-Ph- o-BPinacol] (11), [4-bromo-2,6-di-Me-Ph-N=C(Me)-Py-C(Me)=N-Ph-o-BPinacol] (12), [2,4,6-tri-Me-Ph-N=C(Me)-Py-C(Me)=N-Ph-m-BPinacol](14), [2,4,6-tri-Me-Ph-N=C(Me) -Py-C(Me)=N-Ph-p-BPinacol] (17), and [4-Bromo-2,6-di-Me-Ph-N=C(Me)-Py-C(Me)=N- Ph-p-BPinacol] (18), and their corresponding Fe(II) complexes [{o-PinacolB-Ph-N=C(Me)-Py-C(Me)=N-Ph-o-BPinacol}FeCl2] (3), [{2,4,6-tri-Me-Ph-N=C(Me)-Py-C(Me)=N-Ph-o-BPinacol}FeCl2] (19), [{4-bromo-2,6-di-Me-Ph-N=C(Me)-Py-C(Me)=N-Ph-o-BPinacol}FeCl2] (20), [{2,4,6-tri-Me-Ph-N=C(Me)-Py-C(Me)=N-Ph-m-BPinacol}-FeCl2] (21), [{2,4,6-tri-Me-Ph-N=C(Me)-Py-C(Me)=N-Ph-p-BPinacol}FeCl2] (22), and [{4-bromo-2,6-di-Me-Ph-N=C(Me)-Py-C(Me)=N-Ph-p-BPinacol}FeCl2] (23) were synthesized. According to X-ray analysis, the introduction of boryl groups in the ortho-positions of the complex as in 3 caused the shortening of the axial Fe-N bond lengths (up to 0.02 A) vs the analogous Fe(II) complex with ortho-methyl groups [{o-Me-Ph-N=C(Me)-Py-C(Me)=N-Ph-o-Me}FeCl2], 1. The comparisons of the axial bond lengths in ortho-boryl-substituted isomer 19 with para-boryl-substituted 22 revealed that these bonds are shorter in the ortho-isomer (2.201(11) A) than in the para-isomer (2.232(2) A). An interesting structural feature of 3 is that it exists in the unexpected up-up conformer in the solid state, despite reasonable bulkiness of dioxaboranyl substituents in ortho-positions. Complexes 21-23 afforded very productive catalysts for the production of α-olefins with a more linear Schultz-Flory distribution and with the least amounts of the heavier insoluble fractions of α-olefins than the parent methyl-substituted Fe(II) complex 1.